Fungicidal methods and compositions



United States Patent 3,323,990 FUNGICIDAL METHODS AND COMPOSITIONS Paul B. Budde and Henry Tolkmith, Midland, Mich., assignors to The Dow Chemical Company, Midland Mich., a corporation of Delaware No Drawing. Filed Apr. 29, 1965, Ser. No. 451,983 26 Claims. (Cl. 167-33) The present invention is concerned with imidazolyl phosphorus compounds of the formula and with methods employing and compositions comprising the compounds for the control of fungal organisms. In the above and succeeding formulae, each X substituent independently represents a member selected from the group consisting of hydrogen, loweralkyl, and phenyl, the total number of carbon atoms in all X substituents being an integer of from 0 to 15, both inclusive; and,

(A) each of R and R being taken separately, R represents a member selected from the group consisting of diloweralkylamido and R, and each R' independently represents a member selected from the group consisting of (3) heteroparaffinic amido,

(4) heteroaromatic amido, and

G being a member selected from the group consisting of loweralkyl and G"; G being a member selected from the group consisting of phenyl, loweralkylphenyl, and G"; and G" being a member selected from the group consisting of phenylloweralkyl, (loweralkylphenyl)loweralkyl, furfuryl, tetrahydrofurfuryl, and (4 pyridylmethyl); and,

(B) R and R being taken together, R and R jointly represent a moiety of the formula such radical has a total number of carbon atoms whichis an integer of from 7 to 15, both inclusive. In the instance of the loweralkylphenyl and (loweralkylphenyl) loweralkyl radicals, one or two loweralkyl substituents are present on the phenyl moiety of the radical. The term diloweralkylamido is employed in the present specification and claims to designate a radical of the formula wherein each E independently represents a loweralkyl radical being of from 1 to 4, both inclusive, carbon atoms. The term heteroparafiinic amido is employed in the present specification and claims to describe a radical selected from the group consisting of morpholino, thiomorpholino, piperidino, l-pyrrolidinyl, 4-substituted-lpiperazinyl wherein the substituent is loweralkyl, phenyl,

or acetyl, and 1,2,3,6-tetrahydro-l-pyridyl; and the term:

heteroaromatic amido, to describe a radical of the formula V wherein Q represents a group which with the nitrogen atom completes an aroma-tic ring which (1) has five ring atoms, of which ring atoms at least two are nitrogen and one is carbon each of the two remaining ring atoms being selected from the group consisting of carbon and nitrogen and of which (2) each ring carbon atoms bears a substituent which is selected from the group consisting of hydrogen, lower-alkyl, and phenyl, the total number of carbon atoms in all substituents on all ring carbon atoms of the aromatic ring being an integer of from 0 to 15, both inclusive.

Representative heteroaromatic amido radicals include the following: pyrazol-l-yl; imidazol-I-yl; 1,2,3-triazo1-l yl; 3,5-di-n-propylpyrazol-l-yl; 3-n-butylpyrazol-1-yl; 4,5- di-phenylpyrazol-l-yl; Z-methylimidazol-l-yl; 2-sec butylimidazol-l-yl; 2 phenylimidazol-l-yl; 2-:methyl-4-pheny1- imidazo1-1-yl; 2-phenyl-4 methylimidazol-l-yl; 4,5-diphenylimidazol-l-yl; 4,5-di-n-butylimidazol-l-yl; 2-methyl-' Patented June 6, 1967 The reaction is conveniently carried out in the presence of an inert liquid reaction medium, which is preferably an organic liquid, and in the presence of a hydrogen chloride acceptor. The imidazole compound can be employed both as reactant and as hydrogen chloride acceptor, or any tertiary organic amine, such as triethylamine, can beemployed as hydrogen chloride acceptor. The reaction takes place smoothly at temperatures between and 60 C., and preferably at temperatures between 25 and 60, with the production of the desired imidazolyl phosphorus compound and by-product which appears as the hydrochloride salt of the compound employed as hydrogen chloride acceptor.

Organic liquids which are suitable as reaction media include hydrocarbons, such as benzene, toluene, xylene, and cyclohexane; ethers, such as diethyl ether, 1,2-dimethoxyethane, or tetrahydrofuran; and tertiary amines, such as triethylamine. It is generally preferred to avoid the use as reaction medium of any compound which has a reactive hydrogen, because its use may result in side reactions.

The amounts of the reactants to be employed are not critical, some of the desired product compound being obtained when employing the reactants in any amounts. However, the reaction consumes the reactants in amounts representing equimolecular proportions of phosphorothioic chloride, imidazole compound, and hydrogen chloride acceptor, and the use of amounts which represent such proportions is preferred. When imidazole compound is employed both as reactant and as hydrogen chloride acceptor, the reaction consumes one molecular proportion of phosphorothioic chloride and two molecular proportions of imidazole compound, and the use of the reactants in amounts representing such proportions is preferred.

- In carrying out the reaction, the reactants are contacted together in any convenient fashion and maintained for a period of time in the reaction temperature range. Some of the desired product is formed immediately upon the contacting together of the reactants; however, the yield of the desired product is increased by permitting the reaction mixture to stand for a period of time, preferably with stirring or other mechanical agitation of the mixture. Following the completion of the reaction, the reaction mixture can be employed for the useful purposes of the present invention. However, the desired product compound can be separated from the reaction mixture. In many instances, for example, where the product compound is to be employed for the control of fungal organisms attacking foliage and a phytotoxic compound has been employed as reaction medium, separation is preferable. The separation is carried out in conventional procedures. Most typically, the reaction mixture is filtered to separate the insoluble hydrochloride by-product salt, and organic liquid employed as reaction mixture is moved from the filtrate by evaporation under subatmospheric pressure to separate the desired product. The product so obtained can be used without purification or can be purified by conventional procedures. For example, the separated product can be mixed with a quantity of any of the organic liquids to be employed as reaction medium, the resulting mixture filtered to separate insoluble by-product materials, and the organic liquid removed from the filtered mixture by evaporation under subatmospheric pressure, to obtain the purified product. Also, in the instance of those products which are solids, the separated product can be purified by recrystallization.

The imidazolyl phosphorus compounds can also be prepared in alternative procedures. One of these is suitable for all products wherein not more than one of R and R represent phenyl or styryl. In this procedure, a phosphorothioic dichloride compound having one of the formulae ll diloweralkylamldeP-Cl 1 is reacted, in the presence of the hydrogen chloride acceptor, with an imidazole compound, .as previously defined, to form an intermediate imidazolyl phosphorothioic chloride compound of one of the corresponding formulae This intermediate is thereafter reacted, in the presence of a hydrogen chloride acceptor, with an amino compound to obtain the desired imidazolyl phosphorus compound. In the instance of the compound of Formula la, the amino compound is a reactant of the formula HR wherein R=heteroparafiinic amido, heter-oaromatic amido, or

In the instance of compound of Formula 1111, the amino compound is a reactant of one of the formulae H- and diloweralkylamido-H.

The reactions of this first alternative procedure are conveniently "carried out in a reaction medium of the sort employed in the preparation procedure previously described. The hydrogen chloride acceptor employed in either reaction of the procedure can be an organic tertiary amine; preferably, however, the imidazole compound, or amino compound, respectively, is employed both .as reactant and as hydrogen chloride acceptor. Good results are obtained when employing substantially equimolecular proportions of (1) phosphorothioic dichloride compound, imidazole compound, and hydrogen chloride acceptor, and (2) intermediate, amino compound, and hydrogen chloride acceptor. When imidazole compound and amino compound are employed both as reactant and as hydrogen chloride acceptor, good results are obtained when employing (1) one molecular proportion of phosphorothioic dichloride compound and two molecular proportions of imidazole compound, and (2) one molecular proportion of intermediate and two molecular proportions of amino compound. The first step of the reaction is somewhat exothermic and is carried out at temperatures of from 50 to 25 C. The second step of the reaction is also exothermic and takes place at temperatures of from 10 to 60 C. The temperature can be controlled by regulating the rate of mixing and contacting of the reactants, and by external cooling. The by-p-roduct in both steps is a hydrochloride salt, appearing as the hydrochloride salt of the hydrogen chloride acceptor. Following the reaction, the desired product can be separated in accordance with the conventional procedures described for the first preparation procedure above.

In a second alternative procedure applicable to those products wherein both of R and R represent a heteroaromatic amido group identical with the imidazolyl moiety in the general formula, PSCl is reacted, in the presence of a hydrogen chloride acceptor, with an imidazole compound, as previously defined, to obtain product of the formula The hydrogen chloride acceptor can be any tertiary organic amine, or the imidazole compound can be employed both as reactant and as hydrogen chloride acceptor. The reaction taken place readily at temperatures of from O to 60 C. with the production of the desired product an hydrochloride salt of reaction, which salt ordinarily appears as the hydrochloride salt of the hydrogen chloride acceptor. Upon completion of the reaction, the desired product is separated by the conventional procedures previously defined.

In all preparation procedures hereinabove discussed, the imidazolyl moiety is introduced by reaction of a phosphorus-containing compound, as variously defined, with an imidazole compound, as defined. Similarly, in the instance wherein R is a heteroa-romatic amido radical, such moiety is introduced by reaction of a phosphorus-containing compound with a reactant of the formula HR" where R is heteroaromatic amido, that is, a reactant of the formula: 'heteroaroma-tic amid- H. In the instance of each of the imidazole compound and the heteroaromatic amido-H reactant, such compound ordinarily occurs as a tautomeric form in which no hydrogen is fixably positioned at any given ring-nitrogen atom. Accordingly, in the reaction of certain of these reactants, in the methods hereinabove presented, isomeric products are produced. The products can be separated by such conventional separation procedures as chromatographic separation and fractional crystallization.

The following examples illustrate the best methods now known for the practice of the present invention and will enable those skilled in the art to practice the invention.

Dimethylphosphoramidothioic dichloride (85.0 grams; 0.475 mole) and N-methylaniline (107.0 grams; 1.0 mole) were mixed in 50 millimeters of benzene, and the mixture heated to a temperature of about 100 C. and held there, with stirring, for about eighteen hours. The mixture then was cooled to room temperature and 500 milliliters of benzene added-to the mixture. Thereafter, the mixture was filtered to separate the N-methylaniline hydrochloride and the filtered by-product washed with two 250-milliliter portions of benzene.

The filtrate and wash were combined, containing in combination approximately 0.5 mole of N,N,N'-trimethyl- N'-phenylphosphorodiamidothioic chloride, and imidazole (68.0 grams; 1.0 mole) added to the combined filtrate and wash at a temperature of 23 C. over a period of four hours. Thereafter, the reaction mixture was held, with stirring, at room temperature for fifteen hours and concentrated by evaporation of benzene under subatmospheric pressure. The concentrated reaction mixture was diluted with 500 milliliters of benzene, the diluted mixture filtered to separate imidazole hydrochloride by-product, and the by-product salt washed with 250 milliliters of benzene. The filtrate and wash were combined and concentrated by distillation under reduced pressure to yield the desired P imidazol-1-yl-N,N,N'-trimethyl-N'-phenyl phosphonothioic diamide-product. The product, an oil, was obtained in an 84 percent yield.

Example ZJ-lmidazol-I-yldiphenyl phosphine sulfide Qil F Q Diphenylphosphinothioc chloride (126.3 grams; 0.5 mole) was mixed with 1 liter of benzene. To the resulting mixture, 68 grams of imidazole (1.0 mole) were added portionwise to the mixture over a four and one-half hour period. The addition was carried out with the reaction mixture at a temperature of 2528 C. After the completion of the addition, the reaction mixture was stirred for twelve hours at a temperature of 24-26 C. Thereafter, the reaction mixture was filtered, the imidazole hydrochloride washed with three 250 milliliter portions of henzene, and the filtrate and wash liquid combined and concentrated to obtain the desired imidazol-l-yldiphenyl phosphine sulfide product. The product was obtained in a yield of 89.5 percent and was found to have a melting range of 98-103 C.

Example 3.-Imia'azol-1-yldipiperidino phosphine sulfide Dipiperidinophosphinothioic chloride (67.0 grams; 0.25 mole) and imidazole (34.0 grams; 0.5 mole) were reacted in essentially the same manner as the reactants of Example 2. The imidazol-l-yldipiperidino phosphine sulfide product melted at 76-78 C.

Example 4.2-imidazol-1-yl-1,3-dimethyl-1,3,2- diazaphospholidine-Z-sulfide 2 chloro-1,3-dimethyl-1,3,2-diazaphospholidine-2-sulfide (92.5 grams; 0.5 mole) and triethylamine (70 milliliters; 0.5 mole) were mixed with 250 millilters of benzene. To the resulting mixture, there was added portionwise over a period of one hour 34 grams of imidazole (0.5 mole). The addition was carried out with stirring at room temperature. After the completion of the addition, the reaction mixture was held, for fourteen hours, with stirring, at a temperature of 55-60 C. Thereafter, the reaction mixture was diluted with 250 milliliters of henzene at room temperature, the diluted reaction mixture filtered to separate triethylamine hydrochloride, which was thereafter washed with 250 milliliters of benzene, and the filtrate and wash liquid combined. Benzene was removed from the combined filtrate and wash liquid by evaporation under subatmospheric pressure to obtain the desired 2- imidazol-1-yl-1,3-dimethyl 1,3,2 diazaphospholidine-Z- sulfide product as a residue. The product residue was purified by recrystallization from cyclohexane to obtain a purified product melting at 52 C.

Example 5.Triimidaz0l-1-yl phosphate sulfide Imidazole (102.0 grams; 1.5 moles) and triethylamine (210.0 milliliters; 1.5 moles) were disposed in 1500 milliliters of benzene to prepare a first mixture. Also, PSCl (52.0 milliliters; 0.5 mole) was dispersed in 100 milliliters of benzene to prepare a second mixture. The first mixture was cooled to a temperature of 0-5 C. and the second mixture, was added, with stirring, to the first mixture at 0-5 C. The addition was carried out over a period of 5 hours. After complete addition the slurry was stirred at room temperature for about twelve Name of product: Identifying property p-Imidazol-l-yl N-n-butyl-NN-methyl-p-styryl phosphinothioic amide p-Imidazol 1 yl N,N' dimethyl- N,N' diphenyl phosphonothioic diamide p-Imidazol-l yl N,N dibenzyl-N, N dimethyl phosphonothioic diamide M.P p-Imidazol 1 yl N methyl N,

N',N'-tribenzyl phosphonothioic diamide M.W p-Imidazol l yl N,N diethyl-N'- methyl-N (4-pyridylmethyl) phosphonothioic diamide p,p-DiimidaZol-l-yl N,N di-n-butyl phosphinothioic amide M.-P p,p-Diimidazol-1 yl N furfuryl-N- methyl phosphinothioic amide Diimidazol-l-yl(1,2,3,6 tetrahydro-lpyridyl) phosphine sulfide Oil p-Imidazol-l-yl N,N-dimethyl-p-pyrazol-l-yl phosphinothioic amide Oil In the above table, the symbol M.P. is used as an abbreviation of the term melting point, and the symbol M.W., as an abbreviation of the term molecular weight.

It has been discovered that the present imidazolyl phosphorus compounds are particularly adapted to be employed for the control of a wide range of fungi, especially those fungal organisms ordinarily found on the aerial portions of plants, such as, for example, cherry leaf spot, apple scab, rice blast, powdery mildew, helminthosporium (leaf spot on grasses, cereals, and corn), and late blight. The compounds can also be applied in dormant applications to the woody surfaces of plants or to orchard floor surfaces for the control of the overwintering spores of many fungi. In addition, the imidazolyl phosphorus compounds can 'be applied to seeds to protect the seeds from the attack of fungal organisms such as rot and mildew. Also, the imidazolyl phosphorus compounds can be distributed in soil at fungicidal concentrations to control the organisms which attack seeds and plant roots, particularly the fungal organisms of root rot and mildew.

In further operations, the compounds can be included in inks, adhesives, soaps, cutting oils, polymeric materials, or in oil or latex paints, to prevent mold, mildew, and the degradation of such products resulting from microbial attack. Also, the compounds can be distributed in textile or cellulosic materials, or can be employed in the impregnation of wood and lumber to preserve and protect such products from the attack of the microbial agents of rot, mold, mildew, and decay. The foregoing environments are merely illustrative of the many habitats in which these agents can be distributed to obtain excellent fungal control.

It is an advantage of the present invention that compositions containing these compounds can be applied to growing vegetation in amounts required for effective control without significant injury to the plants. It is a further advantage that the compounds of the present invention are of very low toxicity to mammals. It is another advantage that a single application of the compounds will provide a residual and extended control of fungi over a period of several months. Also, it is an advantage that the imidazolyl phosphorus compounds are effective in eliminating established fungal infestation as well as in providing residual and extended control against fungal attack. Further, the imidazolyl compounds have been found to be translocated in plants and thus it is an advantage -of the present inventions that the compounds provide a systematic protection against the plant attacking organisms. It is a yet further advantage that the imidazolyl phosphorus compounds can be handled with a minimum of danger from accidental mammalian exposure thereto because of their low mammalian toxicity.

Oil

Oil

Oil

Oil

The method of the present invention comprises contacting a fungal organism with a fungicidal amount of one or more of the imidazolyl phosphorus compounds. However, the present invention also embraces the employment of a liquid, powder or dust composition containing one or more of the compounds. Such compositions are adapted to be applied to the living plants without substantial injury to the plants. In preparing toxicant compositions, the imidazolyl phosphorus compounds can be modified with one or more of a plurality of additaments including organic solvents, petroleum distillates, water or other liquid carriers, surface active dispersing agents, and finely divided inert solids. In such compositions, the imidazolyl phosphorus compounds oftentimes are present in a concentration from about 2 to 98 percent by weight. Depending upon the concentration in the composition of the imidazolyl phosphorus compound, such augmented compositions are adapted to be employed for the control of the undesirable fungi or employed as concentrates and subsequently diluted with additional inert carrier to produce the ultimate treating compositions. In compositions where the adjuvant or helper is a finely divided solid, a surface-active agent, or the combination of a surfaceactive agent and a liquid additament, the carrier cooperates with the active component so as to facilitate the invention, and to obtain an improved and outstanding result.

The exact concentration of the imidazolyl phosphorus compound employed in the compositions for application to the fungal organism and/ or its habitat can vary provided a fungicidal dosage of toxicant is applied either on the organism or its environment. This dosage of toxicant is primarily dependent upon the susceptibility of the particular organism to the particular imidazolyl phosphorus compound employed. In general, good results are obtained with liquid compositions containing from about 0.0001 to 2.0 percent by weight of toxicant; in some operations, however, compositions containing as much as from 2 to 98 percent by weight are conveniently employed, as for example, in applications to orchard floor surfaces for the control of spores. With dusts, good results are usually obtained with compositions containing from 0.00 1 to 2.0 percent or more by weight of toxicant. In some circumstances, it is preferred to employ dust compositions containing as much as from 2 to 98 percent or more by weight of toxicant. Where the compositions are to be applied to living plants, it is preferred that the toxicant be present in an amount not to exceed about 0.8 percent in liquid compositions and 1.0 percent in dusts. In terms of acreage application, good controls of fungal organisms are obtained when the imidazolyl phosphorus compounds are applied to plots of growing plants at a dosage of from 0.004 to 3 or more pounds per acre.

In the protection and preservation of inks, adhesives, cutting oils, paints, textiles, and paper, good results are obtained when the compounds are incorporated in such products in the amount of at least 0.0001 percent by Weight. In the preservation of wood, excellent results are obtained when the compounds are incorporated by conventional treatment in the wood in the amount of at least 0.0001 pound per cubic foot of wood.

In the preparation of dust compositions, the toxicant products can be compounded with any of the finely divided solids such as pyrophylite, talc, chalk, gypsum, and the like. In such operations, the finely divided carrier is ground or mixed with the toxicant or wet with a solution of the toxicant in a volatile organic solvent. Similarly, dust compositions containing the products can be compounded with various solid surface-active dispersing agents, such as fullers earth, bentonite, attapulgite and other clays. Depending upon the proportions of ingredients these dust compositions can be employed for the control of fungi or employed as concentrates and subsequently diluted with an additional solid surface-active dispersing agent or with pyrophyllite, chalk, talc, gypsum,

13 and the like to obtain the desired amount-of active ingredient in a composition adapted to be employed for the control of fungi. Also, such dust compositions, when employed as concentrates, can be dispersed in water, with or without the aid of dispersing agents, to form spray mixtures.

Further, the imidazolyl phosphorus compounds or a liquid or dust concentrate composition containing such compounds can be incorporated in intimate mixture with surface-active dispersing agents such as non-ionic emulsifying agents to form spray compositions. Such compositions are readily employed for the control of fungi or are dispersed in liquid carriers to form diluted sprays containing the toxicants in any desired amount. The choice of dispersing agents and amounts thereof employed are determined by the ability of the agents to facilitate the dispersion of the concentrate in the liquid carrier to produce the desired spray compositions.

Similarly, the toxicant products can be compounded with a suitable water-immiscible organic liquid and a surface-active dispersing agent to produce emulsifiable concentrates which can be further diluted with water and oil to form spray mixtures in the form of oil-in-water emulsions. In such compositions, the carrier comprises an aqueous emulsion, i.e., a mixture of water-immiscible solvent, emulsifying agent and water. Preferred dispersing agents Which can be employed in these compositions are oil-soluble and include the non-ionic emulsifiers such as the condensation products of alkylene oxides with the inorganic acids, polyoxyethylene derivatives of sorbitan esters, complex ether alcohols and the like. Suitable organic liquids which can be employed in the composition include petroleum oils and distillates, toluene, and synthetic organic oils. The surface-active dispersing agents are usually employed in liquid compositions in the amount of from 0.1 to 20 percent by Weight of the combined weight of the dispersing agent and active compound.

When operating in accordance with the present invention, the imidazolyl phosphorus compounds or a composition containing the compounds can be applied to the fungal organisms to be controlled, or to their habitats in any convenient fashion, e.g., by means of hand clusters or sprayers. Applications to the above-ground portions of plants conveniently can be carried out with powder dusters, boom sprayers, high-pressure sprayers, and spray dusters. In foliar applications, the employed compositions should not contain any appreciable amount of phytotoxic diluents. In large scale operations, dusts or low volume sprays can be applied from airplanes.

In other operations, the imidazolyl phosphorus compounds can be dispersed in an atmosphere, particularly within a space temporarily or permanently enclosed such as a greenhouse, railroad car, or the like, to control fungal organisms therewithin, to protect contents exposed to the atmosphere, and to control air-borne fungal organisms such as spores and the like. In these operations, an imidazolyl phosphorus compound can be placed upon a surface of which the temperature facilitates volatilization, at a desired rate, of the compound or composition containing the same into the atmosphere also, in an alternate embodiment, an imidazolyl phosphorus compound can be used as an aerosol; a cosolvent, and the resulting composition released from a pressure container into the atmosphere.

The following examples further illustrate the present invention.

Example 6 50 parts by weight of p-imidazol l-yl-N,N-diethyl-pphenyl phosphinothioic amide is mixed and ground with 18 parts of diatomaceous earth (Celite 209), 24 parts of a hydrous aluminum silicate (Barden Clay), 6 parts of an alkyl aryl sulfonate (Nacconol NRSF), and 2 parts of a substituted benzoic alkyl sulfonic acid (Daxad No. 27) to prepare a composition which can be used in accordance with the foregoing teachings. In a similar manner, other compositions are prepared by employing one of the following in place of the p-imidazol-l-yl-N,N-diethyl-p-phenyl phosphinothioic amide:

p-Imidazol-1yl-N,N-dimethyl-p-phenyl phosphinothioic amide;

Diimidazol-l-yl(1,2,3,6-tetrahydro-l-pyridyl) phosphine sulfide; v

Imidazol-l-ylphenylpiperidino phosphine sulfide;

p,p-Diimidazol-1-yl-N,N-dimethyl phosphinothioic amide;

Imidazol-l-yldipiperidino phosphine sulfide; and

p,p-Diimidazol-l-yl-N-n-butyl-N-methyl phosphinothioic amide.

Also, 90 parts by weight of p-imidazol-1-yl-N,N-diethyl-p-phenyl phosphinothioic amide and 10 parts by weight of a sorbitan monolaurate polyoxyethylene derivative (Tween 20) are mixed together to prepare another composition which also can be employed according to the foregoing teachings. In a similar manner, other compositions are prepared by employing one of the following in place of p-imidazol-l-yl-N,N-diethyl-p-phenyl phosphinothioic amide:

Diimidazol-l-ylpiperidino phosphine sulfide;

p,p-Diimidazol-l-yl-N,N-diethyl phosphinothioic amide;

p-Imidazol-1-yl-N,N-dimethyl-p-styryl phosphinothioic amide;..

p,p-Diimidazol-1-yl-N-benzyl-N-methyl phosphinothioic amide;

p-Imidazol-l-yl-N-benzyl-N-methyl-p-(4-methyl-l-piperazinyl) phosphinothioic amide; and

p-Imidazol-1-yl-N-benzyl-N,N',N'-trimethyl phosphonothioic diamide. V

In other procedures, aqueous compositions are prepared by mixing and grinding together in a ballmill 0.06 part by weight of one of the imidazolyl phosphorus compounds, 0.06 part of an alkyl aryl sulfonate (Nacconol NR), 0.06 part of Daxad No. 27, and 200 parts of water.

These compositions are adapted to be employed for the control of fungi or to be dispersed in water to provide aqueous compositions having desirable wetting properties. The compositions are useful for the distribution of the compounds in fungicidal amounts.

Example 7 Four parts by weight of p-imidazol-l-yl-N,N-diethyl-pphenyl phosphinothioic amide, 0.08 part of sorbitan trioleate (Span 85) and 0.02 part of a sorbitan monolaurate polyoxyethylene derivative (Tween are dispersed in 40 milliliters of acetone to produce a concentrate composition in the form of a water-dispersible liquid. A portion of this concentrate composition is dispersed in Water to produce an aqueous spray composition containing 75 parts of the subject compound per million parts by weight of ultimate mixture. The resultant composition is sprayed with an atomizing spray nozzle using air pressure at 20 pounds per square inch on young potato plants which are about 6 inches tall. The applications are carried out so as to give thorough coverage of all surfaces of the leaves of the plants without appreciable run-off. Following the applications, the spray compositions are allowed to dry upon the leaf surfaces and the plants then inoculated by spraying with a suspension of viable spores of Phytophthera infestans (late blight). Untreated potato plants of the same maturity are similarly inoculated to serve as checks. Immediately following the inoculation, all plants are placed in a moist chamber and maintained at 70 F. under saturated humidity conditions for 24 hours. Thereafter, the plants are set aside under greenhouse conditions for about five days and observed for the development of the lesions of late blight caused by the Phytophtheraorganisms to determine the percent control of this organism.

Observation about one week following the inoculations shows substantially complete controls of Phytophthora infestans on the plants sprayed with the composition containing p-imidazol-l-yl-N,N-diethyl-p-phenyl phosphinothioic amide. At the time of the observations, the leaves of the untreated check plants are found to be heavily covered with lesions of Phytophthora infestans.

Example 8 Igarts of Suaject P t K n ompoun per ercen 1 Subject Compound Million Parts and Control of per Weight of Phytophthora Aqueous Spray Infestans P,P-Diimidazol-1-yl-N,N-dimethyl 75 100 phosphinothioie amide 37 100 P-Imidazol-1-yl-N,N-dimethyl-P- 75 100 phenyl phosphinothioic amide 37 100 18 100 I,P-Diimidazol-1-yl-N-n-butyl-N- 150 100 methyl phosphinothioic amide 75 100 Diimidazol-l-ylpiperidino phosphine 9g sulfide 37 98 18 95 Diimidazol-l-ylphenyl phosphine sulfide 75 100 P-Imidazol-l-yl-N-n-butyl-N-methyl- P-phenyl phosphinothioie amide 150 98 P-Imidazol-l-yl-N-furfuryl-N-rnethyl- 150 100 P-phenyl phosphinothioic amide. 75 100 P-Imidazol-l-yl-N,N-dimethyl-P- 150 95 morpholino phosphinothioie amide 75 95 P-Imidazol-l-yl-N-benzyl-N-methyl- 150 95 P-phenyl phosphinothioic amide 75 95 P-Imidazol-l-yl-P-styryl-N,N-diethyl phosphinothioie amide 150 98 P P-Diimidazol-l-yl-N N-diethyl phosphinothioic nmide gg P-Imidazol-l-yl-N-methyl-N-(4- pyridylmethyD-P-phenyl phosphinothioic amide. 75 95 P-Imidazo1-1-yl-N,N- 1 -butyl-P- phenyl phosphinothio c amide 150 100 P,P-Diimidazol-l-yl-N-benzyl-N- methyl phosphinothioic amide 150 100 P-(2-Ethyl-tmethylimidazol-l-yl)- N,N-diethyl-P-phenyl phosphinothioie amide 150 95 ImidazoI-l-ylphenyl(1,2,3,6-tetrahydro-l-pyridyl) phosphine sulfide"... 150 100 P-Imidazol-l-yl-N,N-dibenzyl-N,N- 150 100 dimethyl phosphonothioic diamide 75 100 P-Imidazol-l-yl-N-benzyl-N-methy1- 150 100 P-(4-methyl-1-piperazinyl) phos- 75 98 phinothioic nmide P-Imidazol-l-yl-N,N-dimethyl- -1- pyrrolidinyl phosphinothioic amide. 150 98 Z-Imidazol-l-yl-l,3-dimethyl-1,3,2-

diazaphospholldine-2-sulfide 150 100 Example 9 Spray compositions each containing an amount of one of the imidazolyl phosphorus compounds and each prepared according to Example 7 were employed for the control of Erysiphe cichoracearum, an organism causing powdery mildew on cucumber plants. In such operations, each spray composition was sprayed on cucumber plants through an atomizing nozzle using a pressure of 20 pounds per square inch. The applications were carried out so as to give thorough coverage of all surfaces of the plants. After the spray deposit had dried, the plants were inoculated with spores of Erysiphe cichoracearum. Untreated cucumber plants were similarly inoculated to serve as checks. After 14 days in a greenhouse, the plants were observed for the development of powdery mildew. The imidazolyl phosphorus compounds, the concentrations in the spray composition, and the results of the observations, are set forth in the following table.

The phosphorothioic chloride compounds employed as starting compounds in the preparation of the products of the present invention are prepared by known procedures. For example, in the instance wherein each of R and R is taken separately, and R represents diloweralkylamido and R represents heteroparaffinic amido, heteroaromatic amido, or

PSCl is reacted successively in either order or simultaneously with a compound of the formula diloweralkylamido-H and with a compound of the formula R"H, wherein R represents heteroparaflinic amido, heteroaromatic amido,

When both of R and R represent the same or different heteroparaffinic amido, heteroaromatic amido, or

groups, PSCl is reacted successively in either order or simultaneously with one or more reactants of the RH formula only. It is preferable to carry out either type of reaction in an inert liquid reaction medium and in the presence of a hydrogen chloride acceptor. Preferably, the hydrogen chloride acceptor is the same compound as the R"H or diloweralkylamido-H reactant. Good results are obtained when employing the reactants in amounts which represent equimolecular proportions of PSCl of each reactant from which it is desired to introduce one R or R group into the ultimate phosphorothioic chloride starting material, and of hydrogen chloride acceptor. When both groups to be introduced are the same, good results are obtained when employing two molecular proportions of the reactant from which the group is derived, two molecular proportions of the hydrogen chloride acceptor, and one molecular proportion of PSCl 1 7 Those of the starting phosphorothioic chloride compounds wherein R and R' are taken together are prepared by a modification of this procedure. In this modification, a diamine compound of the formula I N-H E! is reacted with PSCl Good results are obtained when employing one equimolecular proportion of diamine compound, one molecula-r proportion of PSCl and two molecular proportions of hydrogen chloride acceptor. In all other respects, the reaction is carried out as hereinabove set forth.

In the preparation of those starting products wherein each of R and R represents phenyl or styryl, an aromatic compound of the formula Ar-H where Ar represents phenyl or styryl, is reacted with aluminum chloride and phosphorus trichloride (PCl at temperatures of from 50 to 280 C. to prepare a diarylphosphorus chloride product of the formula Ar PC1 and PCI;, by-product. Good results are obtained when employing the reactants in amounts which represent one molecular proportion of aromatic compound, 1.3 molecular proportions of aluminum chloride, and 4 molecular proportions of phosphorus trichloride. The PCl is separated in conventional procedures and the diaryl phosphorus chloride reacted with an excess of PSCl at temperatures of from 50 to 150 C. to prepare thedesired starting product of the formula Starting products wherein one of the R and R' represents phenyl or styryl and the other represents diloweralkylamido, heteroparatfinic amido, heteroaromatic amido, or

are prepared by reacting an arylphosphorous dichloride product of the formula ll A1-PO12 with a compound of the formula RIIIH where R' represents diloweralkylamido, heterop-araflinic amido, heteroaromatic amido, or

described by I. R. Van Wazer in Phosphorus and its Compounds, volume 1, pages 245 and 258 (1958, Interscience Publishers, New York, NY.) and by K. Sasse in Methoden der Organischen Chemie, volume XII, part i, Organische Phosphorverbindungen, pages 387- 406, 552, 557 (1963; Thieme Verlag, Stuttgart, Germany).

The present application is directed to and concerned with the disclosure and claiming of the invention as described hereinbefore. The present application is also directed to the disclosure and claiming of the invention in compounds, methods, or compositions, comprising or employing any subgeneric group or class of imidazolyl phosphorus compounds which may be obtained by any permutation or combination of the alternative expressions in the several compound definitions to be found hereinbefore.

We claim:

1. Method which comprises contacting a fungal organism with a fungicidal amount of an imidazolyl phosphorus compound of the formula wherein each X substituent independently represents a member selected from the group consisting of hydrogen, loweralkyl, and phenyl, the total number of carbon atoms in all X substituents being an integer of from 0 to 15, both inclusive; and

(A) when R and R are taken separately, R represents a member selected from the group consisting of diloweralkylamido and R, and each R independently represents a member selected from the group consisting of (3) heteroparaifinic amido radical selected from the group consisting of morpholino, thiomorpholino, piperidino, l-pyrrolidinyl, 4-substitutedl-piperazinyl wherein the substituent is loweralkyl, phenyl, or acetyl, and 1,2,3,6-tetrahydro- -p y (4) heteroaromatic amido radical of the formula wherein Q represents a group which with the nitrogen atom completes an aromatic ring which (a) has five ring atoms, of which ring atoms at least two are nitrogen and one is carbon, each of the two remaining ring atoms being selected from the group consisting of carbon and nitrogen and of which (h) each ring carbon atom bears a substituent which is selected from the group consisting of hydrogen, loweralkyl, and phenyl, the total number of carbon atoms in all substituents on all ring carbon atoms of the aromatic ring being an integer of from 0 to 15, both inclusive, and

G being a member selected from the group consisting of loweralkyl and G"; Gt being a member selected from the group consisting of phenyl, loweralkylphenyl, and G"; and G" being a member selected from the group consisting of phenylloweralkyl, (l0weralkylphenyl)- loweralkyl, furfuryl, tetrahydrofurfuryl, and (4-pyridylmethyl); and, i r

(B) R and R being taken together, represent a moiety of the formula N I Z! Z being a member selected from the group consisting of o-phenylene and alkylene being of from 2 to 3, both inclusive, carbon atoms; and Z being a member selected from the group consisting of loweralkyl, phenyl, and phenylloweralkyl.

2. The method according to claim 1 wherein said imidazolyl phosphorus compound is employed in the form of a composition comprising said compound in intimate admixture with a parasiticide adjuvant as a carrier thereof.

3. The method of claim 1 wherein the imidazolyl phosphorus compound is p-imidazol-l-yl-N,N-diethyl-p-phenyl phosphinothioic amide.

4. The method of claim 1 wherein the imidazolyl phosphorus compound is p,p diimidazol l yl N benzyl- N-methyl phosphinothioic amide.

5. The method of claim 1 wherein the imidazolyl phosphorus compound is p,p-diimidazol-l-yl-n,N-diethyl phosphinothioic amide.

6. The method of claim 1 wherein the imidazolyl phosphorus compound is p,p-diimidazol-l-yl-N-n-butyl-N- methyl phosphinothioic amide.

7. The method of claim 1 wherein the imidazolyl phosphorus compound is p-imidazol-l-yl-N,N-dimethyl-pphenyl phosphinothioic amide.

8. The method of claim 1 wherein the imidazolyl phosphorus compound is imidazol-l-ylphenylpiperidino phosphine sulfide.

9. The method of claim 1 wherein the imidazolyl phosphorus compound is p-imidazolyl-p-styryl-N,N-dimethyl phosphinothioic amide.

10. The fungicidal com-position comprising an imidazolyl phosphorus compound in intimate mixture with from 0.1 to 20 percent by weight of a surface-active dispersing agent, said imidazolyl phosphorus compound being of the formula R s L I \n i R, X X

wherein each X substituent independently represents a member selected from the group consisting of hydrogen, loweralkyl, and phenyl, the total number of carbon atoms in all X substituents being an integer of from to 15, both inclusive; and,

(A) when R and R are taken separately, R represents a member selected from the group consisting of diloweralkylamido and R, and each R independently represents a member selected from the group consisting of (3) heteroparaflinic amido radical selected from the group consisting of morpholino, thiomorpholino, piperidino, l-pyrrolidinyl, 4-substitutedl-piperazinyl wherein the substituent is loweralkyl, phenyl, or acetyl, and l,2,3,6-tetrahydrol-pyridyl,

(4) heteroarom-atic amido radical of the formula wherein Q represents a group which with the nitrogen atom completes an aromatic ring which (a) has five ring atoms, of which ring atoms at least two are nitrogen and one is carbon, each of the two remaining ring atoms being selected from the group consisting of carbon and nitrogen iand of which (b) each ring carbon atom bears a substituent which is selected from the group consisting of hydrogen, loweralkyl, and phenyl, the total number of carbon atoms in all substituents on all ring carbon atoms of the aromatic ring being an integer of from 0 to 15, both inclusive, and

G being a member selected from the group consisting of loweralkyl and G"; G being a member selected from the group consisting of phenyl, loweralkylphenyl, and G"; and G" being a member selected from the group consisting of phenylloweralkyl, (loweralkylphenyl) loweralkyl, furfuryl, tetrahydrofurfuryl, and (4-pyridylmethyl); and, (B) R and R being taken together, represent a moiety of the formula l N z Z being a member selected from the group consisting of o-phenylene and alkylene being of from 2 to 3, both inclusive, carbon atoms; and Z being a member selected from the group consisting of loweralkyl, phenyl, and phenylloweralkyl.

11. An aqueous dispersion of the composition of claim 10 wherein the imidazolyl phosphorus compound is present in such composition in an amount of at least 0.0001 percent by weight.

12. The composition of claim 10 wherein the imidazolyl) phosphorus compound is p-imidaz0l-1-y1-N,N-diethyl-p-phenyl phosphinothioic amide.

13. The composition of claim 10 wherein the imidazolyl phosphorus compound is p,p-diimidazol-l-yl-N-benzyl-N-methyl phosphinothioic amide.

14. The composition of claim 10 wherein the imidazolyl phosphorus compound is p,p-diimidaz0l-1-yl-N,N- diethyl phosphinothioic amide.

15. The composition of claim 10 wherein the imidazolyl phosphorus compound is p,p-diimidazol-l-yl-N-nbutyl-N-methyl phosphinothioic amide.

16. The composition of claim 10 wherein the imidazolyl phosphorus compound is p-imidazol-1-y1-N,N-dimethyl-p-phenyl phosphinothioic amide.

17. The composition of claim '10 wherein the imidazolyl phosphorus compound is imidazol-l-ylphenylpiperidino phosphine sulfide.

18. The composition of claim 10 wherein the imidazolyl phosphorus compound is p-imidazolyl-p-styryl-N,N- dimethyl phosphinothioic amide.

19. The fungicidal composition comprising from 2 to 98 percent by weight of an imidazolyl phosphorus compound in intimate admixture with a finely divided inert solid, said imidazolyl phosphorus compound being of the formula wherein each X substituent independently represents a member selected from the group consisting of hydrogen, loweralkyl, and phenyl, the total number of carbon atoms in all X substituents being an integer of from to 15, both inclusive; and,

(A) when R and R are taken separately R represents a member selected from the group consisting of diloweralkylarnido and R, and each R independently represents a member selected from the group consisting of (3) heteroparafiinic amido radical selected from the group consisting of morpholino, thiomorpholino, piperidino, l-pyrrolidinyl, 4-substitutedl-piperazinyl wherein the substituent is loweralkyl, phenyl, or acetyl, and 1,2,3,6-tetrahydro- -py y (4) heteroaromatic amido radical of the formula wherein Q represents a group which with the nitrogen atom completes an aromatic ring which (a) has five ring atoms, of which ring atoms at least two are nitrogen and one is carbon, each of the two remaining ring atoms being selected from the group consisting of carbon and nitrogen and of which (b) each ring carbon atom bears a substituent which is selected from the group consisting of hydrogen, loweralkyl, and phenyl, the total number of carbon atoms in all substituentson all ring carbon atoms of the aromatic ring being an integer of from 0 to 15, both inclusive, and

G being a member selected from the group consisting of loweralkyl and G"; G' being a member selected from the group consisting of phenyl,

lower-alkylphenyl, and G"; and G" being a member selected from the group consisting of phenylloweralkyl, (loweralkylphenyl) loweralkyl, furfuryl, tetrahydrofurfuryl, and (4-pyrid ylmethyl); and,

(B) R and R being taken together, represent a moiety of the formula Z being a member selected from the group consisting of o-phenylene and alkylene being of from 2 to 3, both inclusive, carbon atoms; and Z being a member selected from the group consisting of loweralkyl, phenyl, and phenyllowenalkyl.

20. The composition of claim 19 wherein the imidazolyl phosphorous compound is p-imidazol-1-yl-N,N-diethyl-p-phenyl phosphinothioic amide.

21. The composition of claim 19 wherein the imidazolyl phosphorus compound is P,P-diimidazol-l-yl-N-benzyl-N-methyl phosphinothioic amide.

22. The composition of claim 19 wherein the imidazolyl phosphorus compound is p,p-diimidazol-1-yl-N,N-diethyl phosphinothioic amide.

23. The composition of claim 19 wherein the imidazolyl phosphorus compound is p,p-diimidazol-1-yl-N-nbutyl-N-methyl phosphinothioic amide.

24. The composition of claim 19 wherein the imidazolyl phosphorus compound is p-imidazol-1-yl-N,N-dimethyl-p-phenyl phosphinothioic amide.

25. The composition of claim 19 wherein the imidazolyl phosphorus compound is imidazol-l-ylphenylpiperidino phosphine sulfide.

26. The composition of claim 19 wherein the imidazolyl phosphorus compound is p-imidazol-l-yl-p-stylryl- N,N-dimethyl phosphinothioic amide.

References Cited UNITED STATES PATENTS 2,853,416 9/1958 Kellog 16733 2,920,997 1/1960 Wolf 167-33 2,944,601 7/1960 Jacob et a1. 260309 3,111,525 11/1963 Meltzer 260-309 3,111,526 11/1963 Koopmans 260-309 3,120,542 2/1964 Anderson 260-309 ALBERT T. MEYERS, Primary Examiner.

SAM ROSEN, STANLEY I. FRIEDMAN,

Assistant Examiners. 

1. METHOD WHICH COMPRISES CONTACTING A FUNGAL ORGANISM WITH A FUNGICIDAL AMOUNT OF AN IMIDAZOLYL PHOSPHORUS COMPOUND OF THE FORMULA 